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Modern organonickel chemistry 2005 tamaru


Modern Organonickel
Chemistry
Edited by Yoshinao Tamaru

Modern Organonickel Chemistry. Edited by Y. Tamaru
Copyright 8 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 3-527-30796-6


Further Titles of Interest
A. de Meijere, F. Diederich (Eds.)

Metal-Catalyzed Cross-Coupling
Reactions, 2nd Ed., 2 Vols.
2004

ISBN 3-527-30518-1

M. Shibasaki, Y. Yamamoto (Eds.)


Multimetallic Catalysts in Organic
Synthesis
2004

ISBN 3-527-30828-8

M. Beller, C. Bolm (Eds.)

Transition Metals for Organic Synthesis,
2nd Ed., 2 Vols.
Building Blocks and Fine Chemicals
2004

ISBN 3-527-30613-7

S.-I. Murahashi (Ed.)

Ruthenium in Organic Synthesis
2004

ISBN 3-527-30692-7

J.-E. B€ackvall (Ed.)

Modern Oxidation Methods
2004

ISBN 3-527-30642-0


Modern Organonickel Chemistry

Edited by Yoshinao Tamaru


Editor
Professor Dr. Yoshinao Tamaru
Department of Applied Chemistry
Faculty of Engineering
Nagasaki University


1-14 Bunkyo-machi
Nagasaki 852-8521
Japan

Cover Picture
The front cover is showing a Kabuki actor
dressed like a devil, drawn by Sharaku.
Nickel was first isolated in 1751 from an
ore referred to as ‘‘devil Nick copper’’.
Miners named the ore in that way because
it resembled copper ore, but did not yield
their objective copper. (Old Nick, informal
the devil; Satan, from Webster’s Unabridged
Dictionary). Nickel was named after its
accursed nickname. Reproduced with
permission of the Tokyo National Museum.

9 All books published by Wiley-VCH are
carefully produced. Nevertheless, authors,
editors, and publisher do not warrant the
information contained in these books,
including this book, to be free of errors.
Readers are advised to keep in mind that
statements, data, illustrations, procedural
details or other items may inadvertently be
inaccurate.
Library of Congress Card No.: Applied for
British Library Cataloging-in-Publication
Data: A catalogue record for this book is
available from the British Library.
Bibliographic information published by Die
Deutsche Bibliothek
Die Deutsche Bibliothek lists this
publication in the Deutsche
Nationalbibliografie; detailed bibliographic
data is available in the Internet at http://
dnb.ddb.de
( 2005 WILEY-VCH Verlag GmbH & Co.
KGaA, Weinheim
All rights reserved (including those of
translation in other languages). No part of
this book may be reproduced in any form –
nor transmitted or translated into machine
language without written permission
from the publishers. Registered names,
trademarks, etc. used in this book, even
when not specifically marked as such, are
not to be considered unprotected by law.
Printed in the Federal Republic of
Germany.
Printed on acid-free paper.
Typesetting Asco Typesetters, Hong Kong
Printing Strauss GmbH, Mo¨rlenbach
Bookbinding J. Scha¨ffer GmbH, Gru¨nstadt
ISBN-13 978-3-527-30796-8
ISBN-10 3-527-30796-6


v

Contents
Preface

xi

List of Contributors
Abbreviations
1

1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.7.1
1.7.2
1.7.3
1.7.4
1.7.5
1.7.6
1.8

xv

xvii

Introductory Guide to Organonickel Chemistry
Yoshinao Tamaru
The Crystal Field 2
Nickel has Wings: The Mond Method 3
The Ligand Field 3
The Formal Oxidation Number 6
The 16- and 18-Electron Rule 8

1

The Structure, Reactivity, and Electronic Configuration of NickelComplexes 11
The Elementary Reactions 15
Oxidative Addition 15
Insertion 18
Transmetallation 20
Reductive Elimination 23
b-Hydrogen Elimination 26
a- and b-Carbon Elimination (CaC Bond Cleavage) 28
Catalytic Reactions 29
References 37

2

Nickel-catalyzed Cross-coupling Reactions
Tamotsu Takahashi and Ken-ichiro Kanno

2.1

Cross-coupling of Alkyl Electrophiles with Organometallic
Compounds 41
Cross-coupling of Alkenyl Electrophiles with Organometallic
Compounds 45
Cross-coupling of Allyl Electrophiles with Organometallic
Compounds 47

2.2
2.3

41

Modern Organonickel Chemistry. Edited by Y. Tamaru
Copyright 8 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 3-527-30796-6


vi

Contents

2.4
2.5

3

3.1
3.2
3.3
3.4
3.5
3.6

Cross-coupling of Aryl Electrophiles with Organometallic
Compounds 48
Asymmetric Cross-coupling Reactions 53
References 53
Reaction of Alkenes and Allyl Alcohol Derivatives
Yuichi Kobayashi
Hydrovinylation of Olefins 56
Hydrocyanation of Olefins 59
Heck-type Cyclization 60
Olefin Insertion 61

56

Nickel-catalyzed Hydrozincation of Olefins 64
Ni-catalyzed Addition of Organometallics to Electron-deficient
Olefins 65
3.6.1
The Reaction with Organometallics 65
3.6.2
The Reaction with Organic Halides as Nucleophiles 68
3.7
Polymerization of Ethylene and a-Olefins using Ni(II)-based
Catalysts 70
3.8
The Nucleophilic Reactions of p-Allylnickel Complexes 72
3.9
p-Allylnickel Complexes from Enones 74
3.10
Carbonylative Cycloaddition of Allylic Halides and Acetylenes 75
3.11
Nucleophilic Allylation Toward p-Allylnickel Complexes 77
3.11.1 Allylation with Grignard Reagents 77
3.11.2 Allylation with Soft Nucleophiles 80
3.11.3 Regiochemical Control Based on Internal Chelation 80
3.11.4 Organometallics other than Grignard Reagents for Allylation 82
3.11.4.1 Ni-catalyzed Allylation with Lithium Borates Derived from Trimethyl
Borate 82
3.11.4.2 Allylation with Lithium Borates Derived from Acetylene 84
3.11.4.3 Allylation with Borates Derived from Cyclic Boronate Esters 85
3.11.5 The Design of Functionalized Reagents for Allylation 85
3.11.6 Nickel-catalyzed Reactions of Cyclopentenyl Acetate and Borates 87
3.11.7 Synthetic Application of Nickel-catalyzed Reactions of Cyclopentenyl
Acetate and Borates 89
3.11.8 Extension of the Lithium Borate/Nickel Catalyst for Coupling with
Alkenyl and Aryl Substrates 91
3.12
Nickel Enolates 92
3.12.1 Reactions of Ni(II) Complexes with Lithium or Potassium
Enolates 93
3.12.2 The Reformatsky-type Reaction 95
3.12.3 Other Reactions through Nickel Enolates 96
References 97
4

4.1

Reaction of Alkynes 102
Shin-ichi Ikeda
Hydrogenation 103


Contents

4.2
4.2.1
4.2.2
4.2.3
4.2.4
4.3
4.3.1
4.3.2
4.4
4.5
4.5.1
4.5.2
4.5.3
4.5.4
4.6
4.6.1
4.6.2
4.6.3
4.6.4
4.7

Hydrometallation and Related Reactions 104
Hydrosilylation and Hydrostannylation 104
Hydroboration 106
Hydroalumination 107
Miscellaneous: the Addition of HaP and HaS Groups 107
bis-Metallation 107
bis-Silylation and bis-Germylation 108
Silaboration and Geraboration 110
Hydrocyanation, Hydroacylation, and Related Reactions 111
Carbometallation and Related Reactions 113
Carbomagnesiation 113
Carbozincation 114
Carbostannylation 115
Miscellaneous 117
The Sequential Reaction 118
Sequential Reaction Starting with Activation of Organic Halides
Sequential Reaction with Enones 123
Sequential Reaction with Aldehydes and Imines 127
Sequential Reaction with Epoxides 129
Addenda 131
References 132

5

Reaction of Dienes and Allenes 137
Masanari Kimura and Yoshinao Tamaru

5.1
5.1.1

Dimerization and Polymerization of 1,3-Dienes 137
Structure of Ni-(butadiene)2 Complexes Stabilized by Phosphine
Ligands 138
Dimerization of Substituted 1,3-Dienes 139
Ni-catalyzed Polymerization of Butadiene 141
Stereo- and Regioselective Polymerization of Conjugated Cyclic
Dienes 143
Allylation and Homoallylation of Aldehydes with Dienes and
Allenes 143
Allylation of Aldehydes via Dimerization of 1,3-Dienes 143
Allylation of Aldehydes with Dienes Promoted by Silane
(R4Àn SiHn ) 145
Allylation of Aldehydes with Dienes Promoted by Diisobutylaluminum
Hydride (DIBAL) or Diisobutylaluminum(III)(acac) 147
Homoallylation of Aldehydes Promoted by Triethylborane or
Diethylzinc 151
Allylation of Aldehydes Promoted by Dimethylzinc, Trimethyborane, and
Related Compounds: the Three-component Connection Reactions 154
The Multi-component Connection Reaction 157
Cyclization of Allenyl Aldehydes 158
Addition Reaction of HX on Dienes and Allenes 160
Addition of Active Methylene Compounds to 1,3-Dienes 160

5.1.2
5.1.3
5.1.4
5.2
5.2.1
5.2.2
5.2.3
5.2.4
5.2.5
5.2.6
5.2.7
5.3
5.3.1

118

vii


viii

Contents

5.3.2
5.3.3
5.3.4
5.3.5
5.3.6
5.3.7
5.3.8
5.3.9

6

6.1
6.2
6.3
6.3.1
6.3.2
6.3.3
6.3.4
6.3.5
6.4
6.4.1
6.4.2
6.4.3
6.4.4
6.5
6.5.1
6.5.2
6.5.3
6.6

Hydrocyanation of 1,3-Dienes 160
Hydroamination of 1,3-Dienes and Allenes 161
1,4-Dialkenylation of 1,3-Dienes 162
Addition of SiaB and Csp2 aB Compounds on 1,3-Dienes 163
Carbostannylation of 1,3-Dienes and Allenes 164
Carbozirconation of Allenes 166
Wurtz-type Coupling Reaction of Organic Halides and Grignard
Reagents Mediated by the Butadiene–Nickel Complex (5.1) 167
Carbosilylation of Diene Dimers 168
References 168
Cyclooligomerization and Cycloisomerization of Alkenes and Alkynes
Shinichi Saito
Cyclooligomerization of Alkenes 171
Cycloisomerization of Alkenes 174
Cyclooligomerization of Alkynes 175
Cyclotrimerization of Alkynes 175
Co-cyclotrimerization and Cycloisomerization of Alkynes 178

Co-cyclotrimerization of Alkynes with other Unsaturated
Compounds 180
Cyclotetramerization of Alkynes 183
Co-cyclotetramerization of Alkynes 185
Cyclooligomerization of Dienes 185
Cyclodimerization and Cyclotrimerization of 1,3-Butadiene 186
Cyclodimerization and Cyclotrimerization of Substituted
1,3-Dienes 188
Co-cyclooligomerization of 1,3-Dienes 189
Co-cycloisomerization of 1,3-Dienes 191
Cyclooligomerization of Allenes and Cumulenes 192
Cyclooligomerization of Allene (1,2-Propadiene) 192
Cyclooligomerization of Substituted Allenes 194
Cyclooligomerization of Cumulenes 195
Cyclooligomerization and Cycloisomerization of Miscellaneous
Compounds 197
References 198

7

Nickel-mediated and -catalyzed Carboxylation
Miwako Mori and Masanori Takimoto

7.1
7.2
7.3
7.4
7.5
7.6

Nickel-mediated or -catalyzed Carboxylation of 1,3-Diene 205
Nickel-mediated or -catalyzed Carboxylation of Alkyne 211
Nickel-mediated Carboxylation of Alkene 215
Nickel-mediated Carboxylation of Allene 218
Various Nickel-mediated Carboxylations 220
Perspectives 222
References 222

205

171


Contents

8

8.1
8.2
8.2.1
8.2.2
8.2.3
8.3
8.4

Carbonylation and Decarbonylation
Yoshinao Tamaru
Decarbonylation 224

224

Electrochemical Carbonylation 227
Method A: Utilization of CO 228
Method B: Utilization of CO2 as a CO Source 228
Method C: Utilization of Fe(CO)5 as a CO Source 228
Termination of Cascade Reactions by Carbonylation 229
Carbonylation Forming Carboxylic Acid under Phase-Transfer
Conditions 231
References 238

9

Asymmetric Synthesis 240
Ryo Shintani and Tamio Hayashi

9.1
9.2
9.2.1
9.2.2
9.3
9.4
9.4.1
9.4.2
9.5

The Cross-coupling Reaction 240
Allylic Substitution 246
Allylic Substitution by Carbon Nucleophiles 246
Allylic Substitution by Hydride Nucleophiles 249
Hydrocyanation and Hydrovinylation Reactions 250
Reactions of Organometallic Reagents with Aldehydes and Enones 255
Reaction with Aldehydes 255
Reaction with Enones 256
Activation of Carbonyl Compounds for Cycloaddition and Other Related
Reactions 260
The Diels–Alder Reaction 260
The 1,3-Dipolar Cycloaddition Reaction 262
The Ene Reaction and Conjugate Addition Reaction 263
Addition of Nickel-Enolate Intermediates 267
Other Reactions 269
References 269

9.5.1
9.5.2
9.5.3
9.5.4
9.6

10

10.1
10.1.1

Heterogeneous Catalysis
Tsutomu Osawa

273

Heterogeneous Catalysts and Catalytic Reactions 273
Comparison of Heterogeneous and Homogeneous Catalysts and
Catalytic Reactions 274
10.1.2 Reactions over Heterogeneous Catalysts in Liquids 275
10.2
Heterogeneous Ni Catalysts 276
10.2.1 Reactions in the Petroleum Industry 276
10.2.2 Transformation of Organic Functional Groups 278
10.2.2.1 Raney Nickel 280
10.2.2.2 Nickel Boride 282
10.2.2.3 Supported Nickel Catalysts 283
10.3
Asymmetric Syntheses over Heterogeneous Nickel Catalysts 285
10.3.1 Diastereo-differentiating Reactions 285

ix


x

Contents

10.3.2
10.4
10.4.1
10.4.1.1
10.4.1.2
10.4.1.3
10.4.1.4
10.4.2
10.4.3
10.4.3.1
10.4.3.2
10.4.4
10.4.4.1
10.4.4.2
10.4.5

Enantio-differentiating Reactions 286
Tartaric Acid-modified Nickel Catalyst 287
Preparation of the Base Ni Catalyst 288
Raney Ni Catalyst 289
Reduced Ni Catalyst 289
Supported Ni Catalyst 290
Fine Nickel Powder 290
Modification of the Base Nickel Catalyst 291
Enantio-differentiating Hydrogenation over Tartaric Acid-NaBr-modified
Nickel Catalysts 291
Hydrogenation of Functionalized Ketone 292
Hydrogenation of Alkyl Ketones 294
What Happens on the Nickel Surface? 296
Adsorption of a Modifier and a Co-modifier 296
Mechanism of Enantio-differentiating Hydrogenation 298
Concluding Remarks on Tartaric Acid-NaBr-modified Ni Catalysts 302
References 302
Index

306


xi

Preface
The monographs, The Organic Chemistry of Nickel, Volume 1 (1974) and Volume 2
(1975), which were written by P. W. Jolly and G. Wilke, have long been the ‘‘Bible’’
for organonickel chemists. Unfortunately, however, during the past three decades
no books have been published specializing in organonickel [1], whilst in sharp contrast there has been a flood of monographs focusing on organopalladium [2]. As
a measure of academic activity, Figure 1 compares the number of publications
in journals and letters relating to Ni, Pd, and Pt during the past four decades
(SciFinder, searched on 5th March, 2004). Within the last decades, although academic interest in organonickel has clearly fallen, it is still comparable to that in
organopalladium. By contrast, during the last three years in industry, all of the
group 10 transition metals have vied one with another, as demonstrated by the
number of patents relating to Ni, Pd, and Pt (1139, 1173, and 1251, respectively in
2001; 1319, 1320, and 1469, respectively in 2002; and 1268, 1208, and 1481, respectively in 2003).
Nickel and palladium were born under diametrically opposite stars – nickel was
3000

2500

nickel
palladium
platinum

2000

Number

1500

1000

500

0
60

Fig. 1.

65

70

75

80

85

Year 1960–2003

90

95

00

The number of publications in journals and letters (SciFinder, 5, March, 2004).


xii

Preface

Fig. 2. (a) A Kabuki actor dressed like a devil,
drawn by Sharaku (front cover). Reproduced
with permission of Tokyo National Museum.
(b) One of wooden images of Buddhist saints

(a Bosatsu who is a Buddhistic goddess of
wisdom) decollating the wall of Byodo-in, Uji,
Japan. Reproduced with permission of
, 1999.
8

born poor, and palladium to wealth. Nickel was first isolated in 1751 by a Swedish
mineralogist, A. F. Cronstedt (1722–1765), from an ore referred to as ‘‘devil Nick
copper’’. Miners named the ore in that way because it resembled copper ore, but
did not yield their objective copper. (Old Nick, informal the devil; Satan, from Webster’s Unabridged Dictionary). Nickel was named after its accursed nickname (Fig.
2(a)), whereas palladium was discovered in 1803 in South African crude platinum
ore. Palladium was named after Pallas, a name associated with Greek mythology,
the goddess of wisdom (Fig. 2(b)). Nickel has transmigrated repeatedly, and today
– as a result of many studies and discoveries – has been re-incarnated in the shape
of the goddess of wisdom.
The advantage of using Ni as a catalyst is its low cost, which is about one-tenth
to one-fiftieth that of Pd and Pt (see Table 1). However, certain disadvantages of Ni
and its derivatives (e.g., Ni(CO)4 [3], Ni3 S2 ) are associated with toxicity, human carcinogenesis, and skin allergies.
I feel that a book dealing with recent developments in organonickel chemistry
would be beneficial to both organometallic chemists and synthetic organic chemists, alike. This book covers many discoveries which have been made during the
past three decades, and I am very pleased to have received authoritative reviews of
all chapters from experts working at the forefront of organonickel chemistry. These
colleagues are also active researchers in the field of organopalladium chemistry,
and recognize that these two transition metals show many similarities – and indeed many dissimilarities; for example, Ni forms Ni(CO)4 , while Pd never forms


Preface
Tab. 1.

Price comparison of Ni, Pd, and Pt and their dichlorides (Aldrich Catalog, 2004).

EU gÀ1
EU molÀ1

EU gÀ1
EU molÀ1

Ni slug (99.995) a, b

Pd slug (99.95) a, b

Pt slug (99.99) a, b

5.4
317

62.9 [11.6]
6693 [21.1]

83.1 [15.4]
16 212 [51.1]

NiCl2 (99.99)

PdCl2 (99.999)

PtCl2 (99.99)

26.0
3370

120.0 [4.6]
21 277 [6.3]

250.8 [9.6]
66 713 [19.8]

1 euro (EU) = 130 Yen.
a Figures in parenthesis refer to the purity in %.
b Figures in square brackets refer to price rates relative to nickel
compounds.

Pd(CO)4 ; and h 3 -allylnickel is nucleophilic, while h 3 -allylpalladium is electrophilic,
and so on. Consequently, comparisons made sporadically in this book between Ni
and Pd may help the reader to understand more deeply the characteristics of these
metals.
Finally, I would like to acknowledge the assistance of those reviewers who
checked the content of each chapter to minimize errors and enhance the book’s
academic value. The project of publishing this book in its present form began
with an invitation from Wiley-VCH, and I would like also to acknowledge the initiative of Dr. Elke Maase and the cooperation of Carola Schmidt in bringing the
book to fruition. My acknowledgments are also extended to my wife, Keiko, to my
secretary, Kiyomi Nishina, and also to my colleagues, Dr. Shuji Tanaka and Dr.
Masanari Kimura for their help.
Yoshinao Tamaru
December 2004

References
1 (a) M. Lautens, Science of Synthesis,

Vol. 1, Houben-Weyl Methods
of Molecular Transformations;
Organometallics: Compounds with
Transition Metal-Carbon p-Bonds and
Compounds of Groups 10-8 (Ni, Pd, Pt,
Co, Rh, Ir, Fe, Ru, Os), Georg Thieme
Verlag, 2002; (b) E. W. Abel, F. G. A.
Stone, G. Wilkinson, Comprehensive
Organometallic Chemistry II, Vols. 9
and 12, Pergamon, 1995.
2 (a) G. Bertrand, Palladium Chemistry
in 2003: Recent Developments, Elsevier

Science, 2003; (b) E. Negishi,
Handbook of Organopalladium
Chemistry for Organic Synthesis, Vols. 1
and 2, John Wiley & Sons, 2002; (c) J. J.
Li, G. W. Gribble, Palladium in
Heterocyclic Chemistry: A Guide for the
Synthetic Chemist, Elsevier, 2000; (d) B.
Corain, M. Kralik, Special Issue on
Catalysis with Supported Palladium
Metal at the Turn of the 21st Century,
Elsevier Science, 2001; (e) J. Tsuji,
Perspectives in Organopalladium
Chemistry for the XXI Century, Elsevier,

xiii


xiv

Preface
1999; (f ) Y. Yamamoto, E. Negishi,
Recent Advances in Organopalladium
Chemistry: Dedicated to Professors Jiro
Tsuji and Richard F. Heck, Elsevier,
1999; (g) J. Tsuji, Palladium Reagents
and Catalysts: Innovations in Organic
Synthesis, Wiley, 1995; (h) R. F. Heck,
Palladium Reagents in Organic

Syntheses, Academic Press, 1985;
(i) J. Tsuji, Organic Synthesis with
Palladium Compounds, SpringerVerlag, 1980.
3 D. L. Kurta, B. S. Sean, E. P.
Krenzelok, Am. J. Emergency Med.
1993, 11, 64.


xv

List of Contributors
Tamio Hayashi
Kyoto University
Graduate School of Science
Kitashirakawa Oiwake-cho
Sakyo-ku, Kyoto, 606-8502
Japan
Shin-ichi Ikeda
Graduate School of Pharmaceutical
Sciences
Nagoya City University
Tanabe-dori, Mizuho-ku
Nagoya 467-8603
Japan
Ken-ichiro Kanno
Catalysis Research Center and Graduate
School of Pharmaceutical Science
Hokkaido University
Kita 21, Nishi 10, Sapporo 001-0021
Japan
Masanari Kimura
Graduate School of Science and Technology
Nagasaki University
852-8521 Nagasaki
Japan
Yuichi Kobayashi
Department of Biomolecular Engineering
Tokyo Institute of Technology
4259 Nagatsuta-cho
Midori-ku, Yokohama 226-8501
Japan
Miwako Mori
Graduate School of Pharmaceutical Sciences
Hokkaido University
Sapporo 060-0812
Japan

Tsutomu Osawa
Faculty of Science
Toyama University
Gofuku Toyama 930-8555
Japan
Shin-ichi Saito
Department of Chemistry
Faculty of Science
Tokyo University of Science
Kagurazaka, Shinjuku-ku
Tokyo 162-8601
Japan
Ryo Shintani
Kyoto University
Graduate School of Science
Kitashirakawa Oiwake-cho
Sakyo-ku, Kyoto, 606-8502
Japan
Tamotsu Takahashi
Catalysis Research Center and Graduate
School of Pharmaceutical Science
Hokkaido University
Kita 21, Nishi 10, Sapporo 001-0021
Japan
Masanori Takimoto
Graduate School of Pharmaceutical Sciences
Hokkaido University
Sapporo 060-0812
Japan
Yoshinao Tamaru
Department of Applied Chemistry
Faculty of Engineering
Nagasaki University
1-14 Bunkyo-machi
Nagasaki 852-8521
Japan


xvii

Abbreviations
d
r
1 , 2 , 3
AcOÀ
acac
AO
aq
BINAP
bpy
Bu
Bz
Bzl
CAN
cat
cat M
CN
CHD
COD (cod)
COT (cot)
CDT (cdt)
Cp*
Cp
Cy (c-Hex)
D
DBU
DIBAL
dþ , dÀ
diglyme
DMA
DMAD
DME
DMF

Multi-step reactions
Vacant site on transition metal
Primary, secondary, tertiary
Acetate ion
Acetylacetonate
Atomic orbital
Aqueous
2,2 0 -Bis(diphenylphosphino)-1,1 0 -binaphthyl
2,2 0 -Bipyridyl
n-Butyl
Benzoyl; PhCO
Benzyl; PhCH2
Ceric ammonium nitrate
Catalyst
Catalytic reaction with respect to the Metal (over reaction
arrows)
Coordination number
Cyclohexadiene
1,5-Cyclooctadiene (when used as a ligand)
1,3,5,7-Cyclooctatetraene (when used as a ligand)
1,5,9-Cyclododecatriene (when used as a ligand)
Pentamethylcyclopentadienyl; C5 Me5
Cyclopentadienyl; C5 H5
Cyclohexyl
Crystal field splitting
1,8-diazabicyclo[5.4.0]undec-7-ene
Diisobutylaluminum hydride
Partial positive, negative charge
Diethylene glycol dimethyl ether (MeOCH2 CH2 OCH2 CH2 OMe)
N,N-Dimethylacetamide
Dimethyl acetylenedicarboxylate
1,2-Dimethoxyethane
Dimethylformamide


xviii

Abbreviations

DMG
DMI
DMPE (dmpe)
DMSO
dn
DPPB (dppb)
DPPE (dppe)
DPPEN
DPPF (dppf )
DPPP (dppp)
ds, d p
e
ee
en
Eq.
equiv.
Et
h
HBpz3
HOMO
HMPA
c-Hex
Hex
i-Bu
i-Pr
IR
k
KHDMS
L
LUMO
m
mMe
MAO
MLn
MO
MS
Ms
NBD (nbd)
NMP
NMR
NOE
Np
Nu
OAcÀ

Dimethyl glyoxime
1,3-Dimethylimidazolidinone
1,2-Bis(dimethylphosphino)ethane (when used as a ligand)
Dimethyl sulfoxide
Electron number in d orbital
1,4-Bis(diphenylphosphino)butane (when used as a ligand)
1,2-Bis(diphenylphosphino)ethane (when used as a ligand)
cis-1,2-Bis(diphenylphosphino)ethylene
1,1 0 -Bis(diphenylphosphino)ferrocene (when used as a ligand)
1,3-Bis(diphenylphosphino)propane (when used as a ligand)
d Orbital with s; p symmetry
Electron (as in 18e rule)
Enantiomeric excess
Ethylenediamine; H2 NCH2 CH2 NH2
Equation
Equivalent
Ethyl
Hapticity in p-bonding ligands
Tris (pyrazolyl)borate
Highest occupied molecular orbital
Hexamethylphosphoric triamide
Cyclohexyl
n-Hexyl
iso-Butyl
iso-Propyl
Infrared
Hapticity in s-bonding ligands
Hexamethyldisilazane potassium salt (KN(SiMe3 )2 )
Generalized ligand a 2e neutral ligand (e.g., PPh3 , pyridine)
Lowest unoccupied molecular orbital
Descriptor for bridging
Meta
Methyl
Methylaluminoxane: -[Al(Me)O]n Generalized metal fragment with n ligands (L)
Molecular orbital
Molecular sieves
Methanesulfonyl: CH3 SO2 À
Norbornadiene (when used as a ligand)
N-Methylpyrrolidone
Nuclear magnetic resonance
Nuclear Overhauser effect
Neopentyl
Nucleophiles
Acetate anion


Abbreviations

o-Tol
Ph
phen
pin
PFS
PMB
PPTS
Pr
i-Pr
pro-R, or -S
Py (py)
R
RCM
ROMP
Sia
sec-Bu
TASF
TBAF
TBDMS
TBDPS
t-Bu
TDMPP
Tf
TFP (tfp)
THF
THP
TIPS
TMEDA (tmeda)
TMM
TMP
TMS
Ts
TsOH
X

o-Tolyl: 2-methylphenyl
Phenyl
1,10-Phenanthroline
Pinacolate: OCMe 2 CMe 2 O
p-Fluorostyrene
p-Methoxybenzyl: 4-CH3 OC6 H4 CH2 Pyridinium p-toluenesulfonate
Propyl
iso-Propyl
Stereochemical descriptor
Pyridine (when used as a ligand)
Alkyl group
Ring-closing metathesis
Ring-opening metathesis polymerization
Siamyl: 1,2-dimethylpropyl
secondary Butyl
Tris(diethylamino)sulfonium fluoride
Tetrabutylammonium fluoride
tert-Butyl(dimethyl)silyl
tert-Butyldiphenylsilyl
tertiary Butyl
Tri(2,6-dimethoxyphenyl)phosphine
Trifluoromethanesulfonyl
Tri(2-furyl)phosphine (when used as a ligand)
Tetrahydrofuran
Tetrahydropyran
Tri(isopropyl)silyl
N,N,N,N-Tetramethyl-1,2-diaminoethane (when used as a
ligand)
Trimethylenemethane
2,2,6,6-Tetramethylpiperidine
Trimethylsilyl
Tosyl; p-toluenesulfonyl; p-CH3 C6 H4 SO2
p-Toluenesulfonic acid; p-CH3 C6 H4 SO3 H
Generalized a 2e anionic ligand (e.g., ClÀ )

xix


1

1

Introductory Guide to Organonickel Chemistry
Yoshinao Tamaru

Most organic chemists may be embarrassed and intrigued when they encounter
the type of reaction described in Eq. (1.1). In organic chemistry, most CaC bonds
are formed or cleaved by making use of, more or less, polarized functional groups,
for example, CbO, CaO, and C–halogens. Ethylene is lacking in these ordinary
functionalities and has only the double bond as a reactive group. Consequently,
these chemists may ask themselves: ‘‘What is happening here? Does the process
proceed via a radical reaction or a [2þ2]cycloaddition followed by ring opening?’’

2 H2C CH2

cat Ni, AlR3

H
H

H

ð1:1Þ

H

This reaction, which marks the cornerstone for the flourishing development of
transition metal-catalyzed reactions and their use in industry, was discovered by
chance – as with many other great discoveries – by Ziegler (who was awarded the
Nobel Prize for chemistry in 1963), Wilke, and their coworkers while investigating
the production of polyethylene and ethylene oligomers (C6 aC8 ) promoted by organolithiums and organoaluminums [1]. These investigators found that 1-butene was
obtained exclusively instead of the expected ethylene oligomers, but also noted that
contaminants such as nickel and acetylene changed the course of the reaction
(today these are referred to as ‘‘nickel effects’’; see Section 1.6.3 and Schemes 1.26
and 1.27). At the same time, these researchers realized the uncovered potential of
transition metal catalysis in organic transformations and, after conducting many
tests with a wide range of transition metals, they established the protocol of lowpressure polyethylene production based on the titanium-alkylaluminum catalytic
system.
The aim of this chapter is to outline the basic concepts in the coordination
chemistry as well as the elementary processes and basic reaction patterns in
nickel-catalyzed synthetic reactions. Together, these may help the reader to understand the content of the following chapters, which describe much more sophisticated reactions than that shown in Eq. (1.1).
Modern Organonickel Chemistry. Edited by Y. Tamaru
Copyright 8 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 3-527-30796-6


2

1 Introductory Guide to Organonickel Chemistry

dx2-y 2


y

z

z


dxy
∆o

3d

z

z



Nin+L4
Nin+L6
(octahedral) (square planar)

dxy

dyz

dxz

dxz

z

x

y



Nin+L4
(tetrahedral)

x

y

x

dyz



Nin+



∆t

dz 2

x

x
y

y
dz 2

dx 2-y 2

z

z

L
L

L
L

L
y

Ni
L

L

L

Ni

L

L

y

L
x

L

L

x

L

y
(a)

(b)

x

Ni

(c)

Fig. 1.1. Schematic presentation of the d orbital splitting in
the crystal fields of an octahedral (a), a square planar (b), or a
tetrahedral (c) environment.

1.1

The Crystal Field

If one imagines a nickel atom or its ions isolated in space, it has the five degenerated d orbitals (dxy; dyz; dxz; dx 2 - y 2 , and dz 2 ), all lying at the same energy level. As
six ligands (represented here with L, such as ClÀ , NH3 , and H2 O) approach the
nickel from the Gx;Gy, and Gz directions to form an octahedron, the d orbitals
split into two groups, ds and dp (Fig. 1.1(a)). The orbitals of ds group (dx 2 - y 2 ; dz 2 ,
the orbitals with the s bonding character) that point toward the L groups are
greatly destabilized by electrostatic repulsion and move to a higher energy position.
The dp group orbitals (dxy; dyz; dxz, the orbitals with the p bonding character), on
the other hand, are less destabilized because these orbitals point away from L. The
magnitude of the energy difference (designated by D and called the ‘‘crystal field
splitting’’ or the ‘‘ligand field splitting’’) between the ds and dp groups depend on
the charges on Ni and L and the distance between them.
If the two Ls move away along the z axis, the other four Ls on the Gx;Gy axes
will move closer to the central Ni, and this results in a square planar complex. The
expected energy change of the d orbitals is shown in Figure 1.1(b), where the orbitals that possess the x and y components (dxy; dx 2 - y 2 ) rise, while those possessing
the z component (dz 2 ; dxz) fall. The energy diagram of a tetrahedral complex is


1.3 The Ligand Field

shown in Figure 1.1(c), where those orbitals dsðdz 2 ; dx 2 - y 2 Þ that spread along x; y,
and z axes are apparently away from L and stabilize, whereas dp are all in touch
with L and destabilize. The relative energy levels of ds and dp orbitals are reversed
between the octahedral and tetrahedral complexes.
The energy levels in Figure 1.1 are drawn deliberately for all the octahedral,
square planar and tetrahedral complexes to have the identical energy to that of the
isolated Ni(0), the orbitals of which are fully occupied with 10e. For d 8 Ni(II), a
square planar complex is likely most favored, as the 8e occupy from the most
stable dxz up to the dxy orbitals, leaving the most unstable dx 2 - y 2 orbital unoccupied. This is in accord with the structures that many Ni(II) complexes display
(e.g., Me 2 Ni(PR3 )2 , [Ni(CN)4 ] 2À ).

1.2

Nickel has Wings: The Mond Method

In the industrial process of Na2 CO3 production (the Solvay soda process, 1865),
erosion of the nickel bulb of CO2 lines in an unduly short time period was a serious problem. Mond, in 1890, discovered that metallic nickel, although being a very
hard solid with a high melting point (1455  C), reacted with CO (a small contaminant of CO2 in the above process) to form gaseous Ni(CO)4 (b.p. 43  C, extremely
poisonous) at ambient temperature. He also found that Ni(CO)4 decomposed at
over 180  C, depositing Ni metal. This unique reaction of Ni and CO has been utilized even today as the industrial refining method of metallic nickel (the Mond
method). In fact, nickel is the only metal that reacts with CO at room temperature
and at atmospheric pressure of gaseous CO [2]. Having been greatly impressed by
the demonstration of the above transformations, one of Mond’s contemporaries
noted, philosophically, that ‘‘Mond gave wings to a metal’’ [3].

1.3

The Ligand Field

Why does nickel react with CO so easily? Why is Ni(CO)4 formed selectively, and
not Ni(CO)3 or Ni(CO)5 ? To address this question, the idea of the ligand field is
useful. The model makes up matching pairs between the nine atomic orbitals of
Ni (the five 3d, the one 4s, and the three 4p atomic orbitals) and the molecular orbitals of CO. The most straightforward – but somewhat approximate – explanation
is as follows. The C and O atoms of CO hybridize to make two sp-orbitals. One electron each of C and O atoms is then used to make a sp-s bond, and the two sets of
lone pair electrons of C and O reside on their sp-hybridized orbitals. The one electron on each of the 2p orbitals of C and O forms a p bond, and the two 2p electrons
on O interact with the empty 2p orbital of C to form a charged p bond (Fig. 1.2(a)).
On the other hand, the one 4s and the three 4p orbitals of an Ni mix to make up the
four empty sp 3 -hybridized orbitals. The combination of the four empty sp 3 orbitals

3


4

1 Introductory Guide to Organonickel Chemistry

-

+
C O

Ni
sp 3
empty

sp
filled

σ-bonding
(a)

Ni

+
C
(b)

Fig. 1.2.

O

Ni

C O


filled

π*
empty

π-bonding
(c)

Ni

C

O

(d)

The s (a and b) and p-bonding interaction (c and d) between an Ni and CO.

of the Ni and the four sets of the sp lone pair electrons on the C of four CO provides the four bonding and the four anti-bonding molecular orbitals of the NiaCO
bond (s and s à orbitals; Fig. 1.3). This process is similar to producing tetrahedral
methane (CH4 ) from the sp 3 -hybridized C and the 1s orbitals of four hydrogen
atoms. The difference between these reactions is that in the case of methane, the
carbon bears four valence electrons and each hydrogen one valence electron, and
these form the four covalent bonds. In contrast, in the case of Ni(CO)4 the nickel
bears no valence electrons in the sp 3 orbitals: the two electrons of the NiaCO sbond are donated from the C; hence the s-bond should be ionic in nature (NiÀ aC)
as depicted in Figure 1.2(b).
In addition to the s-bonding, there operates another bonding mechanism, socalled ‘‘back bonding’’ or ‘‘back donation’’. As is illustrated in Figure 1.2(c), the
p à orbital of the CO has a proper symmetry with the dp atomic orbital of the Ni,
and these two interact to each other to make up a new p-bonding orbital, lower in
energy than the dp atomic orbital (and at the same time, a p à anti-bonding orbitals
higher in energy). In the case of Ni(CO)4 , the three p-bonding and the three p à anti-bonding molecular orbitals form (Fig. 1.3). Owing to mismatch of symmetry,
the ds orbitals cannot interact with the pp à orbital of CO and so remain at the
same energy level. The p à orbital of the CO is empty and the dp orbital of an Ni
is filled, so the d electrons of the Ni flow into the p à orbital of CO (back donation).
This mechanism operates so effectively that CO is sometimes called a ‘‘p-acid ligand’’. In all, the donation of 2e from the C atom (s-bonding) and the back donation of 2e from the Ni (p-bonding) result in the formation of a formal NibC double
bond (Fig. 1.2(d)). The reader should note that each CO possesses two p à orbitals,
which makes CO as a strong p-acid ligand. For clarity, only one of the two p à orbitals is depicted in Figure 1.2(c).
The back donation significantly perturbs the electronic structure of CO, filling
electrons in the anti-bonding p à orbital and rendering the bond long and weak. In


1.3 The Ligand Field
σ∗-antibonding

4p (0e)

3

4s (0e)

1

3d (10e) 5

Ni

π∗-antibonding

4 (0e)

3 (0e)
1 (0e)

non-bonding

4 (0e) π*

2 (4e) dσ

π-bonding

3 (6e) dπ

σ-bonding

4 (8e)
Ni(CO)4

4 (8e) n

4 C O

Orbital interaction between an Ni(0) and four CO
that forms 4s bonding (8e), 3p bonding (6e) and two nonbonding (4e) molecular orbitals. All anti-bonding orbitals are
empty. Values indicated beside the energy levels refer to the
number of the orbitals.

Fig. 1.3.

this way, in general, the ligands coordinating to metals can be polarized and elongated, and therefore activated toward chemical reactions, the s and p bonds in the
ligands can be weakened or broken, and chemical bonds can be made or broken
within and between different ligands. This rich pattern of the activation of ligands
is a characteristic feature of organometallic chemistry.
Figure 1.3 illustrates how the whole system, composed of an Ni (left) and
four CO (right), is energetically stabilized by forming tetrahedral Ni(CO)4 . That is,
all the four sets of lone pair electrons on the C of CO are accommodated in the
low-lying sp 3 s-bonding orbitals, and the 6e of 10d electrons of an Ni are in the
low-lying p-bonding orbitals.
The other sets of hybridization of the one 4s and the three 4p of an Ni, for example, (sp 2 þ pÞ forming 3 sp 2 and 1p atomic orbitals, are apparently more unfavorable than the sp 3 hybridization, because a s-bond makes a stronger bond and is
more stable in energy than a p-bond – that is, the more the number of s-bonds
the more stable the complexes. This is the reason why Ni(CO)4 is formed selectively, and not Ni(s-CO)3 or Ni(s-CO)3 (p-CO). Then why is Ni(CO)5 not formed?
This is simply because an Ni is already saturated and no atomic orbitals are available to interact with the fifth CO.

5


1 Introductory Guide to Organonickel Chemistry

6

1.4

The Formal Oxidation Number

It is sometimes very useful to assign a formal oxidation number to carbon and
some heteroatoms that are frequently outside the octet rule, such as N, P, and S
in organic molecules. For this, we impose an ionic model on the compound by artificially disconnecting it into an ion pair. In doing this, each electron pair in any
bond is assigned to the most electronegative of the two atoms that constitute the
bond. Some examples are shown in Scheme 1.1. The oxidation number of carbon
ranges from 4À (e.g., methane) to 4þ (e.g., carbon dioxide). All the reactions in
which the oxidation number is increased (making bond with oxygen or electronegative elements or losing hydrogen) are oxidations. The reverse processes are
reductions. So, as shown in the Eq. (a) of Scheme 1.1, each of all the steps from
carbon dioxide to methane is 2e reduction, and each of the reverse processes from
methane to carbon dioxide is 2e oxidation.

2H

HO

-2H

4+

-O

2H

H

O

O C O
H
2+

O
+O

H

-2H

0

H
H
H
2-

-O

H

OH

H
(a)

C
+O

H

H
4H

2H H H
H
(b)
C
C
B
H
-2H H
-2H H
0
0
24Scheme 1.1. The count of the formal oxidation number.
Figures indicate the formal oxidation number of carbon (Eqs.
(a) and (b)) and boron (Eq. (c)).
2H

3H

C

-3H

H
H

B

B

H

(c)

H
H 3+

In organometallic chemistry, a confusing matter arises because most metal elements are less electronegative (or more electropositive) than H (Table 1.1). Hence,
as shown in Eqs. (b) and (c) of Scheme 1.1, in contrast to the formation of methylcarbene and methane from atomic C and 2H and 4H are 2e and 4e reduction, respectively, the formation of BH3 from an atomic B and 3H is 3e oxidation, as we
disconnect BH3 as one B 3þ and three HÀ , that is, bond formation with H is reduction for an C, but it is oxidation for an B. The dotted trigonal line of B2 H6 in Eq.
(c) of Scheme 1.1 indicates that the three atoms, B, H, and B, form a three-center–
two electron bond.
The idea of oxidation number provides a convenient way to determine the stoichiometric amounts of the reagents required in a variety of oxidation and reduction
reactions. For example, as is shown in Eq. (a) of Scheme 1.2, for the oxidation of an
alcohol with chromium(VI) reagents, balancing the formal oxidation number of
the starting materials and the products shows that 2/3 mol of Cr(VI) are necessary
to oxidize 1 mol of an alcohol to an aldehyde or a ketone. For the reduction of nitrobenzene to azobenzene with zinc dust under alkaline conditions, the amount of


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